Anthraquinone dyes containing a 2-aryloxy alkoxy carbamate moiety, their intermediates, and a process for their preparation

ABSTRACT

IN WHICH A is a monocyclic, bicyclic or tricyclic aryl radical; B is halogen, lower alkyl, lower alkylmercapto, amino, lower alkylamino, di-lower alkylamino or phenylamino, n is an integer of from 0 to 4; each of R1, R2, R3 and r4 is hydrogen lower alkyl, cycloalkyl or phenyl; alternatively, R3 and R4 taken together with the nitrogen atom to which they are attached may be a 5 or 6 membered heterocyclic ring optionally interrupted by oxygen or another nitrogen atom; X is SO3H or hydrogen; and m is an integer of from 1 to 4. The new compounds in which X is SO3H are prepared by reacting an anthrarufindisulfonic acid of the formula   WITH A NEW INTERMEDIATE ARYLOXY ALKOXY CARBAMATE COMPOUND OF THE FORMULA   in the presence of boric and concentrated sulfuric acids, treating the reaction mixture with ammonium hydroxide, and subsequent acidification. Compounds in which X is hydrogen are prepared from compounds of Formula I (X SO3H) by treatment with sodium hydrosulfide. The new anthraquinone compounds of this invention are useful for dyeing synthetic fibers such as polyester, polyamide, acetate or triacetate. New dyestuff compounds having the structure

United States Patent Chang [4 1 Aug. 19, 11975 ANTHRAQUINONE DYES CONTAINING A Z-ARYLOXY ALKOXY CARBAMATE MOIETY, THEIR INTERMEDIATES, AND A PROCESS FOR THEIR PREPARATION Charles H. Chang, Piscataway, NJ.

GAF Corporation, New York, NY.

Dec. 20, 1971 Inventor:

Assignee:

Filed:

Appl. No.:

[52] US. Cl. 260/247.1 A; 260/247.2 B; 260/268 TR; 260/272; 260/293.62;

Int. Cl C07d 87/46 Field of Search 260/377, 247.1 A, 293.62,

260/326-347, 268 TR, 247.2 B, 326.4, 272

Primary E.raminer-Donald G Daus Assistant Examiner-Jose Tovar Attorney, Agent, or FirmWalter C. Kehm [57] ABSTRACT New dyestuff compounds having the structure in which A is a monocyclic, bicyclic or tricyclic aryl radical; B is halogen, lower alkyl, lower alkylmercapto, amino, lower alkylamino, di-lower alkylamino or phenylamino, n is an integer of from 0 to 4; each of R R R and R4 is hydrogen lower alkyl, cycloalkyl or phenyl; alternatively, R and R4 taken together with the nitrogen atom to which they are attached may be a 5 or 6 membered heterocyclic ring optionally interrupted by oxygen or another nitrogen atom; X is 50 1-1 or hydrogen; and m is an integer of from 1 to 4. The new compounds in which X is SO;,H are prepared by reacting an anthrarufindisulfonic acid of the formula on o NHR2 with a new intermediate aryloxy alkoxy carbamate compound of the formula (B) n III. [A] 0 R3 0 (Cl-1 -OCN\ in the presence of boric and concentrated sulfuric acids, treating the reaction mixture with ammonium hydroxide, and subsequent acidification. Compounds in which X is hydrogen are prepared from compounds of Formula I (X=SO;,H) by treatment with sodium hydrosulfide. The new anthraquinone compounds of this invention are useful for dyeing synthetic fibers such as polyester, polyamide, acetate or triacetate.

16 Claims, No Drawings ANTHRAQUINONE DYES CONTAINING A Z-ARYLUXY ALKOXY CARBAMATE MOIlETY, THEIR INTERMEDIIATES, AND A PROCESS FOR THEIR PREPARATION This invention relates to new anthraquinone dyestuffs, to a new process for their preparation, and to their use as dyes for various synthetic fibers. It also relates to new intermediates used in the manufacture of these dyestuffs.

1 ,5-dihydroxy-4,8-diamino-2(p-alkoxyphenyl )anthraquinones are disclosed in U.S. Pat. No. 1,652,584 as being dyestuffs. The use of these compounds as dye stuffs for snythetic fibers was more recently disclosed in U.S. Pat. Nos. 3,265,460 and 3,043,646. These compounds have very satisfactory heat fastness and, in general, possess very desirable dyeing properties. Though these anthraquinone dyestuffs have good light, heat and washing fastness properties as compaared with other known anthraquinone blue dyestuffs, the requirements for modern dyestuffs, due to more severe textile processing conditions encountered in imparting durable press properties to textiles, result in much higher standards than were previously necessary.

More recently, a new class of anthraquinone dyestuffs containing an N-monosubstituted urethane moiety on the 2-phenyl group was disclosed in British Patent Specification No. 1,156,125. These anthraquinone dyes were prepared from the reaction the corresponding 2-(p-hydroxyphenyl) anthrarufin derivatives with organic isocyanates. The patent, however, was devoid of any teaching of anthraquinones containing an N,N- disubstituted urethane moiety or compounds in which the carbamate moiety is not directly linked to the phenyl group.

A new class of anthraquinone dyestuffs has now been discovered which has been shown to possess excellent dyeing properties. These dyestuffs are compounds of the formula:

R NH O OH n n R O(CH -0-C-N m X R 4 OH O NHR in which A is a monocyclic, bicyclic or tricyclic ayrl radical; B is halogen, lower alkyl, lower alkylmercapto, amino, lower alkylamino, di-lower alkylamino or phenylamino; n is an integer of from 0 to 4; each of R R R and R is hydrogen, lower alkyl, cycloalkyl or phenyl; alternatively, R and R taken together with the nitrogen atom to which they are attached may be a 5 or 6 membered heterocyclic ring optionally interrupted by oxygen or another nitrogen atom; X is SO H or hydrogen; and m is an integer of from 2 to 4.

In Formula I, A is peferably phenyl but may also be naphthyl anthracenyl or phenanthryl. The symbol n preferably represents 0 or 1, especially 0. The groups represented by R R R and R are preferably hydrogen or lower alkyl, especially hydrogen, methyl and ethyl. R and R are preferably taken separately but, when taken together form with the nitrogen atom to which they are attached, heterocyclic radicals such as pyrrolidino, piperidino, piperazino and morpholino. The symbol m preferably represents 2.

The term lower alkyl when used herein represents alkyl groups having from 1 to 5 carbon atoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, etc. The term cycloalkyl represented saturated cyclic alkyl groups having from 3 to 6 carbon atoms, including cyclopropyl, cyclopentyl, and cyclohexyl.

Compounds of formula I in which X is SO H are prepared by reacting the corresponding anthrarufindisulfonic acid derivative of the formula R NH 0 on 1 I w/ 503E HO 5 I 3 OH 0 NHR2 with an aryloxy alkoxy carbamate compound of the formula:

In (B).

It is essentially a three step reaction. The first step consists of reacting the anthrarufindisulfonic acid and the carbamate compound in a strongly acid medium comprising concentrated sulfuric acid and boric acid. The anthrarufindisulfonic acid and the boric acid are first dissolved in concentrated sulfuric acid; the weight ratio of boric acid to anthrarufindisulfonic acid may range from about 1:1 to about 10:1, preferably from about 2:1 to about 4:1. The carbamate compound is then added to the solution in slight molar excess. The solu tion is then stirred slowly at a temperature of from about 30C. to about 20C., preferably about l0C.

After this reaction is complete, the mixture is drowned in an aqueous alkali solution at a final pl-I between about 8.5 and 9.5. Preferably, the pH range should be between about 9.0 and 9.5. Ammonium hydroxide is the preferred reagent for use in this alkalization step, although sodium hydroxide and potassium hydroxide may also be used. After this pH adjustment, the mixture is heated under reflux, for approximately 1 hour, filtered and then washed with water. The resultant product is obtained in good yield.

In order to prepare the new compounds in which X is hydrogen, the sulfonic acid derivative, produced according to the foregoing discussion, is further desulfonated with sodium hydrosulfite. This desulfonation process takes place preferably at a temperature of between about 60C. to about 90C. preferably from about to about C. As a result of this third step,

a compound of Formula I in which X is hydrogen is ob tained in excellent yield.

The fact that compounds of Formula I can be obtained by this process is quite surprising since it would normally be expected that the urethane moiety would be cleaved by the strong acids and alkalis used. The process is specific to the production of 2-aryloxy alkoxy carbamate derivatives. For example, it is possible to prepare Z-phenoxy alkoxy carbamate derivatives of anthraquinone dyes, but attempts to prepare 2- phenoxy carbamate derivatives of these dyes by the same process have not been successful.

The compounds of Formula Ill are new compounds. They may be conveniently prepared from aryloxy alcohols according to the following reaction scheme, which is illustrative of the preparation of phenoxy ethyl carbamate:

OCH CH OH NuNCO CF -COOH Further details, reaction conditions, time, etc., may be found in Fieser and Fieser, Reagents For Organic Synthesis 1219 (1967).

Among the specific dyestuff compounds of this invention are those having the following structural formula.

TAB LE Continued R3 H2),. f No. X R, R

SO H H CH OCH CH- OCONHCH 56 H 57 SO H H H OCH CH OCONHCH 58 H SC H :x

59 SO H H CH; OCH CH OCONHCH 60 H 6 l SO H CH H OCH CH OCONH 62 H P he n yl 63 SO H H H OCH CH OCONHCH 64 H 65 SO H H H Q OCH2CH2OCON 66 H 67 so H H H 68 H 69 SO3H H H 71 so H H H OCH CH OCON o 72 H 2 2 The dyestuffs of the present invention are applied to fibers by forming an intimate mixture of the dyestuff with water and, preferably, a dispersing agent. Suitable dispersing agents are lignosulfonates such as sodium lignosulfonate, naphthalene sulfonic acidformaldehyde condensation products or cresol-formaldehyde-sodium sulfite condensation products. The dyestuffs are applied to fibers such as polyester, polyamide, acetate, triacetate or polyolefin fibers by immersion of fabrics or yarns prepared from such fibers in an aqueous dispersion of the dyestuffs. The dyeing may be conducted under pressure and at an elevated temperature for time sufficient for the dye to adhere to the fiber, e.g., 5 minutes to 2 hours. The dyebath may contain dye carriers such as trichlorobenzene, or phenphenylphenol or methylnaphthalene. Likewise a small but effective amount of a surface active agent may also be present in the dyebath.

The following examples are presented to illustrate the spirit, but not to limit the scope, of the present invention.

EXAMPLE 1 To a flask containing a mixture of 30 g of 1,5- diamino-4,8 dihydroxy-anthraquinone-3,7-disulfonic acid and 10 g of boric acid dissolved in 180 ml of 96% sulfuric acid, was added to 10C. in portions 14 g of N-methyl-Z-phenoxyethyl carbamate and stirred at 10C. for 20 minutes. The resulting mixture was drowned to a mixture of 1.5 l. of water (5C) and 480 ml. of cone. NH OH. The alkaline mixture was heated under reflux for three-fourths hour and made acidic with sulfuric acid at C. The mixture was filtered and washed with water at 25C. to give the product with the following structure:

OCH7CH2O-C-NHCH3 o NH This product dyed nylon and wool in bright blue shades with excellent fastness properties.

EXAMPLE IV The monosulfonic acid anthraquinone of Example [I] The monosulfonicg acid anthraquinone prepared in was treated according to the method described in Ex- Example I was slurried with 1.5 l. of water heated to ample IL The product had the Structure 70C. to which 10 ml. of come. 40% methylamine and ml. of 50% NaOH were then added to the resulting This product dyed nylon and wool in bright blue shade with excellent fastness properties.

EXAMPLE lI mixture was added 17 g of sodium hydrosulfite and 20 H N O OH heated at 85C. for 1% hours. The mixture was then u v 9 made acidic with sulfuric acid at 80C., filtered and CH washed with hot water till colorless to give a product 2 2 3 which was dispersed and dyed on polyester fibers in bright blue shade with excellent fastness properties. Ho O NHCH The product consists principally of 3 H N 0 OH O OCH CH OC-NHCH3 The product was dispersed and dyed on polyester fibers and gave a bright blue shade with excellent fastness properties.

n HO O NR EXAMPLES V and VI When N-methyl-phenoxyethyl carbamate was re- EXAMPLE placed by N-ethylphenoxyethyl carbamate in Example Following the method of Example I using, as reacl and treated according to the methods taught in Examtants, lmethylamino-5-amino-4,S-dihydroxyanthraples l and II, the products are V II t OCli Cl-l OC Nl lc ll HO O NR ii ig Q on 3 m OCli Cll OC-NHC H and HO 0 \H quinone-3,7-disulfonic acid and N-methyl-2- The second product (Example VI) dyed polyester in phenoxyethyl carbamate, a compound of the following bright blue shade with good light and sublimation faststructure was obtained ness 5370.226

ff E 0 EXAMPLES VII and VIII OCH CH OCNHCH When N,N-dimethyl-phenoxyethyl carbamate was used to replace N-methylphenoxyethyl carbamate in 3 HO NHCH Example I and the procedures of Example I and II were 3 followed and the following d es were obtained:

I OCH CH -OC-N(CH H Ho I O NH H N O OH 2 v I I 0 d @ocn cn o c N(CH 2 II no 0 EXAMPLES IX and X What is claimed is: When N-methyl phenoxyethyl carbamate in Example A Compound of the formula R NH O OH B) n 3 R O-(CH O- -N 3 X 4 OH 0 NHR2 Iwas replaced y P y y carbamate and the P in which A is a phenyl, naphthyl, anthracenyl or phecedures of Examples I and II were followed, the follow" 3 nanthryl radical: B is hydrogen, lower alkyl, lower aling dyes were obtained. kylmercapto, amino, lower alkylamino, di-lower alkyl H N O OH O 2 I II I i: v

I OCIl CH2-OLl\li2 HO O NH O 11 N 0 m 2 v. 1

/ Q -*JLn Lh -OL=\H II I HO O NH The second product (Example X) dyed pglyester i a amino, halogen or phenylamino; is an integer of from bright blue Shade with good fasmess l to 4; each ofR,, R R and R is hydrogen, lower alkyl, cycloalkyl of 3 to 6 carbon atoms or phenyl; alter- EXAMPLES X1 n X11 natively, R and R taken together with the nitrogen atom to which they are attached form a heterocyclic Wh 16 of 0 en g A ring selected from the group consisting of pyrrolidine, I, piperidine, piperazine, and morpholine; X is SO H or hydrogen; and m is an integer of from 1 to 4. is used instead of the N-methyl2-phenoxyethyl carba- A Compound acording to Claim 1 having the mate in Example I, the following dyes were prepared: mula n I OH O Nll O i l l (I? OCll, Cll,,O-C-N 7 l a a and H I HO O Nh 13 14 R NH on (B R ccn CH -OE-N 3 OH O N'HR in which each of R R R and R is hydrogen or lower 6. A compound according to claim 3 which has the alkyl, or R and R taken together with the nitrogen formula atom to which they are attached are pyrrolidino, piperidino, piperazino or morpholino; and n is O or 1 3. A compound according to claim 2 having the for- 2 9 9 mula R NH 0 on I n I I n I OH O NHCH OCH CH OC-N 7. A compound according to claim 3 which has the formula in which each of R R R and R is hydrogen or lower alkyl. u n 0 on 4. A compound according to claim 3 which has the formula 0 on I I! V I n I OH 0 NHCH I 40 3 OH O NH 1 9 CH O c MlCH OCH CH O-C-NHCH 8. A compound according to claim 3 which has the formula 5. A compound according to claim 3 which has the formula HZN O OH OH O NH 15 16 9. A compound according to claim 3 which has the 13. A compound according to claim 3 which has the formula formula O OH 5 I u H N O OH I II I HO 0 in I II I 2 OH O- NH o OCl-l Cl-I O--C--NH OCH CH O-CNHC H 10. A compound according to claim 3 which has the 14. A compound according to claim 2 which has the formula formula H N O OH u B 14 0 on I N I 3 l n a I.

OH O NR OH N8 0 a u H O c ocn cn o C-N (CH 2 2 2 P 11. A compound according to claim 3 which has the 15. A compound according to claim 2 which has the formula formula H 1? 3 9H 9 9H I u I OH O NH OH O NH O O I II I OCH cu O-C-N (CH H CH O-c-N b 12. A compound according to claim 3 which has the 16. A compound of the formula formula H N O RlNH 0 OH H LIJH HC 0 N H 2 OH O NHR (B) n 9 l l 9 3 OCH CH OCNH O-(Cl O-CL I R R and R taken together with the nitrogen atom to which they are attached, form a heterocyclic ring selected from the group consisting of pyrrolidine, piperidine, piperazine and morpholine and m is an integer of from 1 to 4. 

1. A COMPOUND OF THE FORMULA
 2. A compound acording to claim 1 having the formula
 3. A compound according to claim 2 having the formula
 4. A compound according to claim 3 which has the formula
 5. A compound according to claim 3 which has the formula
 6. A compound according to claim 3 which has the formula
 7. A compound according to claim 3 which has the formula
 8. A compound according to claim 3 which has the formula
 9. A compound according to claim 3 which has the formula
 10. A compound according to claim 3 which has the formula
 11. A compound according to claim 3 which has the formula
 12. A compound according to claim 3 which has the formula
 13. A compound according to claim 3 which has the formula
 14. A compound according to claim 2 which has the formula
 15. A compound according to claim 2 which has the formula
 16. A compound of the formula 